EP2613756B1 - Oral care compositions for benefiting teeth - Google Patents

Oral care compositions for benefiting teeth Download PDF

Info

Publication number
EP2613756B1
EP2613756B1 EP11707437.7A EP11707437A EP2613756B1 EP 2613756 B1 EP2613756 B1 EP 2613756B1 EP 11707437 A EP11707437 A EP 11707437A EP 2613756 B1 EP2613756 B1 EP 2613756B1
Authority
EP
European Patent Office
Prior art keywords
oral care
care composition
teeth
phosphate
calcium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP11707437.7A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP2613756A2 (en
Inventor
Yan Deng
Guanjun Ding
Xiaoke Li
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP2613756A2 publication Critical patent/EP2613756A2/en
Application granted granted Critical
Publication of EP2613756B1 publication Critical patent/EP2613756B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/25—Silicon; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241—Containing particulates characterized by their shape and/or structure
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/24—Phosphorous; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/27—Zinc; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/29—Titanium; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P1/00—Drugs for disorders of the alimentary tract or the digestive system
    • A61P1/02—Stomatological preparations, e.g. drugs for caries, aphtae, periodontitis
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41—Particular ingredients further characterized by their size
    • A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60—Particulates further characterized by their structure or composition
    • A61K2800/61—Surface treated
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60—Particulates further characterized by their structure or composition
    • A61K2800/65—Characterized by the composition of the particulate/core
    • A61K2800/651—The particulate/core comprising inorganic material

Definitions

  • the present invention is directed to an oral care composition for benefiting teeth. More particularly, the invention is directed to an oral care composition that results in, at the very least, the remineralization and whitening of teeth by delivering calcium and phosphate sources to the teeth of consumers when, for example, brushing teeth (i.e., in situ ).
  • the composition is stable and comprises composite particle actives that interact with phosphate ions to produce calcium and phosphate in situ reaction products that surprisingly adhere well to enamel of teeth to ensure excellent whitening results.
  • the composition when for example a toothpaste or gel, maintains good taste, texture and viscosity characteristics, and results in teeth that are less sensitive, and have excellent shine characteristics.
  • the composition can also yield excellent anti-bacterial results within the mouth of consumers after being used as well as immediate whitening benefits.
  • Acidic drinks and sweets can result in tooth erosion by attacking enamel that coats and protects the teeth. Such an attack on enamel often, and undesirably, causes hypersensitivity of the teeth.
  • foods and beverages we consume like tomato sauce, berries, beets, soda or pop, coffee and tea can stain teeth and thereby result in a smile that is not bright and white.
  • Tobacco based products and certain medications can also lead to teeth that look yellow or even brown. Of course, teeth that are not healthy can lead to bad breath and the growth of unwanted bacteria in the mouth.
  • Products that address tooth decay and/or whitening have been developed. Such products often comprise peroxides, abrasives or both in order to clean and whiten teeth. These types of products are often not desired since they do not contribute to the remineralization of teeth and can cause damage to teeth and gums if overused. Products comprising calcium sources have been developed in an attempt to enhance the characteristics of teeth. Such products, however, do not positively adhere to teeth and thereby may only contact teeth for a brief period prior to being rinsed out of the mouth in wash water.
  • This invention is directed to a stable composition that comprises actives suitable to adhere to the enamel of teeth.
  • the composition is stable and maintains good taste, texture and viscosity characteristics when, for example, formulated as a toothpaste or gel composition.
  • Such a composition unexpectedly, results in teeth that are less sensitive and have excellent shine characteristics.
  • the composition can also yield excellent anti-bacterial results within the mouth of consumers after being used, reduce gingivitis as well as freshen and provide immediate whitening benefits.
  • the oral care composition of the present invention can allow for more efficient use of active ingredients.
  • the present invention is directed to an oral care composition
  • an oral care composition comprising:
  • the present invention is directed to a packaged oral care product comprising the oral care composition of the first aspect of this invention.
  • the present invention is directed to a method for whitening the teeth of an individual by using the composition of the first aspect of this invention.
  • Soluble and insoluble refers to the solubility of a source (e.g., like calcium) in water.
  • Soluble means a source that dissolves in water to give a solution with a concentration of at least 0.1 moles per liter at room temperature.
  • Insoluble means a source that dissolves in water to give a solution with a concentration of less than 0.001 moles per liter at room temperature.
  • Slightly soluble therefore, is defined to mean a source that dissolves in water to give a solution with a concentration of greater than 0.001 moles per liter at room temperature and less than 0.1 moles per liter at room temperature.
  • Oral care composition means a composition suitable for use in the mouth and for veterinary and/or human applications but especially for use in applications for the human mouth.
  • Benefitting teeth means at the very least whitening, remineralization or desensitizing teeth or decreasing bacteria within the mouth where the decreasing of bacteria can be the result of employing an antimicrobial agent and the desensitizing of teeth is the result of composite particle active interacting with phosphate ions found in the mouth and/or within the oral care composition and adhering to the teeth to, for example, yield new hydroxyapatite formation. Diameter is meant to mean the longest distance measurable in the event the composite particle active is not a perfect sphere.
  • Remineralization means the in situ generation of hydroxyapatite on teeth to reduce the likelihood of tooth decay and improve the appearance of teeth by whitening through the generation of such new hydroxyapatite. Such remineralization also results in whitening of teeth, all of which can include results from the adhering of composite particle active to the teeth and/or the formation of amorphous calcium phosphate on teeth.
  • Single-phase composition means a one phase composition having both calcium and phosphate sources therein and prior to dispensing or unpackaging and use.
  • Anhydrous as used herein, means substantially free of water (e.g., no water to less than 5% by weight water and preferably less than 1% by weight water).
  • Dual-phase product means having required and complementary calcium and phosphate hydroxyapatite precursors in separate compositions and stored in separate compartments.
  • Composition as used herein includes, for example, paste, powder, gel, liquid (like mouthwash), spray, foam, balm, a composition carried on a mouthstrip or a buccal adhesive patch, chewable tablet (or pastille), lozenge, cream, beverage or a strip of gum.
  • the composition is a paste like toothpaste or a gel for teeth.
  • Carrier as used herein, means a component in the composition other than the composite particle active and phosphate source whereby the carrier is suitable to deliver the active and any phosphate source present therein.
  • First component core is meant to include the portion of the composite particle active that is coated whereby the core can comprise particle or an aggregate of particle like, for example, an agglomerate of TiO 2 .
  • Core is also meant to include a component that can provide immediate (e.g., within three (3) uses of the composition, but preferably, within 1 second to 5 minutes of using) whitening benefits to teeth via physical mechanisms.
  • Long term benefit is meant to include a benefit that will last at least for weeks, but preferably at least four (4) months.
  • the core is meant to be a component that may improve a characteristic of teeth.
  • Second component coating means a coating that forms an external coat or clad on at least a portion of the first component core.
  • adhering can include effectively depositing and/or bonding or "sticking" to teeth as a result of calcium in the coating of the composite particle active and phosphate ion interactions.
  • Coating is also meant to include a component that provides benefits to teeth over time through biological or chemical mechanisms like the formation of hydroxyapatite.
  • Composite particle active therefore, is meant to mean a particle that may provide both immediate and long term benefits to teeth after use.
  • In situ reaction product means a product comprising calcium and phosphate generated in the mouth.
  • the core of the composite particle active comprises a material suitable to physically and immediately improve characteristics of teeth, and especially, whiten teeth.
  • core materials that are suitable to physically improve teeth comprise silica, titanium dioxide, zinc oxide, mica (including coated mica like commercially available iron oxide coated mica), calcium carbonate, barium sulfate or a mixture thereof.
  • the core of the composite particle active typically makes up from 3 to 98%, and preferably, from 6 to 65%, and most preferably, from 10 to 55% by weight of the composite particle active, based on total weight of the composite particle active and including all ranges subsumed therein.
  • the core is at least 50% by weight titanium dioxide, and most preferably, from 60 to 100% by weight titanium dioxide, based on total weight of the first component core.
  • the coating suitable to adhere to tooth enamel, dentin or both typically comprises the element calcium, and optionally, other metals like potassium, sodium, aluminum, magnesium, as well as mixtures thereof whereby such optional other metals are provided as, for example, sulfates, lactates, oxides, carbonates or silicates.
  • the same is suitable to provide a biological or chemical improvement to teeth which is long term (e.g., results in hydroxyapatite formation).
  • the coating employed comprises at least 50% by weight elemental calcium, and most preferably, at least 65% by weight elemental calcium based on total weight of metal in the coating.
  • the metal in the coating is from 80 to 100% by weight elemental calcium, based on total weight of metal in the second component coating and including all ranges subsumed therein.
  • the core and the coating are slightly soluble or insoluble in water, but most preferably, insoluble in water.
  • At least 5% of the outer surface of the core is coated with coating, and preferably, at least 50% of the core is covered with coating. In a most preferred embodiment, 70 to 100% of the outer surface area of the first component core is coated with the second component coating.
  • the diameter of the composite particle active is often from 10 nm to less than 50 microns, and preferably, from 75 nm to less than 10 microns. In an especially preferred embodiment, the diameter of composite particle active is from 100 nm to 5 microns, including all ranges subsumed therein. In yet another especially preferred embodiment, at least 40%, and preferably, at least 60%, and most preferably, from 75 to 99.5% of the diameter of the composite particle active is the result of core, including all ranges subsumed therein.
  • the oral care composition of this invention usually comprises from 0.25 to 40%, and preferably, from 0.5 to 20%, and most preferably, from 0.5 to 15% by weight composite particle active, based on total weight of the oral care composition and including all ranges subsumed therein.
  • the composition comprises an overall metal (e.g., calcium ion) content of less than 40%, and preferably, less than 30%, and most preferably, from 1 to 25% by weight metal, based on total weight of the composition and including all ranges subsumed therein.
  • composite particle active may be added along with an additional metal source like a calcium source.
  • an additional metal source may be identical to that which is used to coat the core of the composite particle active (e.g., calcium silicate or calcium oxide).
  • the additional metal source typically makes up from 0.1 to 35%, and preferably, from 1 to 25%, and most preferably, from 10 to 20% by weight of the total weight of the oral care composition and including all ranges subsumed therein.
  • the second component coating comprises calcium silicate.
  • the coating can comprise the element calcium which originates from insoluble calcium silicate, present as the composite material calcium oxide-silica (CaO-SiO 2 ) as described in commonly-owned applications, World Application Nos. 2008/015117 and 2008/068248 .
  • the ratio of calcium to silicon may be from 1:10 to 3:1.
  • the Ca:Si ratio is preferably from 1:5 to 2:1, and more preferably, from 1:3 to 2:1, and most preferably, from about 1:2 to 2:1.
  • the calcium silicate may comprise monocalcium silicate, bi-calcium silicate, or tri-calcium silicate whereby ratios of calcium to silicon (Ca:Si) should be understood to be atom ratios.
  • the preferred material employed in this invention to deliver calcium and generate second component coating on the composite particle active may be in a crystalline or amorphous state.
  • the material to deliver calcium for the coating is in a mesoporous state, i.e. the source is a material having pores with diameters from 1 nm to 1 micron.
  • Mesoporous calcium silicate (MCS) is often preferred.
  • the MCS which may be used in second component coating in this invention can be made by combining a calcium salt (e.g., calcium chloride, calcium carbonate, calcium hydroxide), a silica precursor like silicate (e.g., sodium silicate, potassium silicate, tetraethyl orthosilicate or tetraethyl silicate)and a structure-directing agent to yield a solid suitable for calcinating.
  • a calcium salt e.g., calcium chloride, calcium carbonate, calcium hydroxide
  • silica precursor like silicate e.g., sodium silicate, potassium silicate, tetraethyl orthosilicate or tetraethyl silicate
  • a structure-directing agent e.g., sodium silicate, potassium silicate, tetraethyl orthosilicate or tetraethyl silicate
  • coating may be formed from CaO-SiO 2 .
  • the oral care composition for benefitting teeth of this invention further comprises a phosphate source.
  • the phosphate source that may be used in this invention is limited only to the extent that the same may be used in a composition suitable for use in the mouth.
  • Illustrative examples of the types of phosphate source suitable for use in this invention and added along with the composite particle actives described include monosodium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium pyrophosphate, tetrasodium pyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate, potassium dihydrogenphosphate, trisodium phosphate, tripotassium phosphate, mixtures thereof or the like.
  • the phosphate source is preferably one which is water soluble.
  • the phosphate source When used, the phosphate source typically makes up from 0.5 to 22%, and preferably, from 2 to 18%, and most preferably, from 4 to 16% by weight of the oral care composition, based on total weight of the oral care composition and including all ranges subsumed therein.
  • the phosphate source used is one which results in an oral care composition (i.e., combined composition if a dual phase product) having a pH from 5.5 to 8, preferably from 6 to 7.5, and most preferably, about neutral.
  • the phosphate source used is trisodium phosphate and monosodium dihydrogen phosphate at a trisodium phosphate to monosodium dihydrogen phosphate weight ratio of 1:4 to 4:1, preferably 1:3 to 3:1, and most preferably, from 1:2 to 2:1, including all ratios subsumed therein.
  • compositions for benefitting teeth described herein may comprise optional ingredients which are common in the art. These ingredients include:
  • Such ingredients typically and collectively make-up less than 20% by weight of the oral care composition, and preferably, from 0.0 to 15% by weight, and most preferably, from 0.01 to 12% by weight of the oral care composition, including all ranges subsumed therein.
  • Thickener may also be used in this invention and is limited only to the extent that the same may be added to a composition suitable for use in the mouth along with the composite particle actives of this invention.
  • Illustrative examples of the types of thickeners that may be used in this invention include, sodium carboxymethyl cellulose, hydroxyl ethyl cellulose, methyl cellulose, ethyl cellulose, gum tragacanth, gum Arabic, gum karaya, sodium alginate, carrageenan, guar, xanthan gum, Irish moss, starch, modified starch, silica based thickeners including silica aerogels, magnesium aluminum silicate (i.e., Veegum) Carbomers (cross-linked acrylates) and mixtures thereof.
  • silica based thickeners including silica aerogels, magnesium aluminum silicate (i.e., Veegum) Carbomers (cross-linked acrylates) and mixtures thereof.
  • sodium carboxymethyl cellulose and/or a Carbomers is/are preferred.
  • a Carbomer those having a molecular weight of at least 700,000 are desired, and preferably, those having a molecular weight of at least 1,200,000, and most preferably, those having a molecular weight of at least about 2,500,000 are desired.
  • Mixtures of Carbomers may also be used herein.
  • the Carbomer is Carbopol ® 980. It has been described as a high molecular weight and cross-linked polyacrylic acid and identified via CAS number 9063-87-0. The same is available commercially from Lubrizol Advanced Materials, Inc.
  • the sodium carboxymethyl cellulose (SCMC) used is SCMC 9H. It has been described as a sodium salt of a cellulose derivative with carboxymethyl groups bound to hydroxyl groups of glyucopyranose backbone monomers and identified via CAS number 9004-32-4. The same is available from suppliers like Alfa Chem.
  • Thickener typically makes up from 0.01 to about 10%, and preferably, from 0.1 to 8%, and most preferably, from 1.5 to 6% by weight of the oral care composition, based on total weight of the oral care composition and including all ranges subsumed therein.
  • Suitable carriers that may be employed in this invention are, for example, glycerin, sorbitol, propylene glycol, dipropylene glycol, diglycerol, triacetin, mineral oil, polyethylene glycol (preferably, PEG-400), alkane diols like butane diol and hexanediol, ethanol, pentylene glycol, or a mixture thereof.
  • the carriers should, in any case, be substantially free of water, and preferably, anhydrous if a single phase product comprising phosphate as an additive and composite particle active are desired.
  • the carrier can, for example, be used in solid form, but glycerin is often the preferred carrier or humectant in single phase products.
  • the carrier is used to take the balance of the single phase compositions up to 100%, and the same may be present in the range from 10 to 90% by weight of the single phase oral care composition.
  • carrier makes up from 25 to 80%, and most preferably, from 45 to 70% by weight of the single phase oral care composition, based on total weight of the single phase oral care composition and including all ranges subsumed therein.
  • a dual phase oral care composition is recommended to prevent interaction (prior to use) between the phosphate and second component coating of the composite particle active.
  • each composition within the dual phase oral care composition comprises less than 35% by weight water, and most preferably, from 15 to 25% by weight water, based on total weight of each composition and including all ranges subsumed therein.
  • compositions within the dual phase oral care composition may be applied to the teeth, with treatment of the teeth involving mixing of the compositions.
  • the compositions are preferably left on the teeth following application.
  • the oral care compositions of this invention should typically be left on the teeth for 5 seconds to 10 hours and more typically from 15 seconds to 6 hours, and most typically, from 35 seconds to 30 minutes.
  • the application may be carried out daily. If a dual composition is employed, the same may be applied from independent compartments at a dual compartment tube or from independent phases of a product contained within a single container which is typically a tube.
  • the means of delivery may optionally involve a tape, in particular an adhesive tape strip, onto which the compositions of this invention are applied prior to the strip being placed in contact with the teeth.
  • a tape in particular an adhesive tape strip
  • the compositions can be held in close contact with the surface of the teeth, facilitating a high concentration of composite particle active and phosphate close to the surface of the teeth.
  • the same typically comprises a polymeric matrix, and is more typically a hydrogel.
  • the polymeric matrix is typically present at from 1 to 25% by weight of the composition of which it is a part.
  • Monomers used to prepare hydrogels may be selected from, for example, vinyl alcohol and acrylate, in particular sodium acrylate. Other monomers comprising an abundance of hydrophilic groups may also be used.
  • hydrogels comprise a polysaccharide, polyacrylamide, polyacrylic acid, or a mixture thereof.
  • Suitable polysaccharides may be storage polysaccharides, such as starch or glycogen, or structural polysaccharides, such as cellulose or chitin.
  • Illustrative polysaccharides which may be used include those having saccharide units selected from one or more of the following: isomaltose, glucose, fructose, galactose, xylose, mannose, sorbose, arabinose, rhamnose, fucose, maltose, sucrose, lactose, maltulose, ribose, lyxose, allose, altrose, gulose, idose, talose, trehalose, nigerose, kojibiose, and lactulose.
  • hydrogels comprise at least one polysaccharide selected from the group consisting of: tamarind gum, guar gum, locust bean gum, Tara, Fenugreek, Aloe, Chia, Flaxseed, Psyllium seed, quince seed, xanthan, gellan, welan, rhamsan, dextran, curdlan, pullulan, scleroglucan, schizophyllan, chitin, hydroxyalkyl cellulose, arabinan, de-branched arabinan, arabinoxylan, glactan, pectic galactan, galactomannan, glucomannan, lichenan, mannan, pachyman, rhamnogalacturonan, acacia gum, agar, alginates, carrageenan, chitosan, clavan, hyaluronic acid, heparin, inulin, cellodextrins, cellulose, and cellulose derivatives.
  • Especially preferred hydrogels can comprise polysaccharides like those selected from the group consisting of: sodium alginate, hydroxypropyl alginate, gum carrageenan, gum arabic, guar gum, karaya gum, chitosan and pectin.
  • compositions of this invention are prepared by conventional methods of making oral care compositions. Such methods include mixing the ingredients under moderate shear and atmospheric pressure.
  • the compositions are desired for use in the mouth, and preferably, are of the form that may be brushed onto teeth with a toothbrush.
  • the oral care compositions of this invention result in excellent remineralization of teeth (i.e., new hydroxyapatite formation) and teeth whitening (which may be immediate and provided for by the core of the composite particle active) as a result of composite particle active adhering to enamel and/or dentin of teeth.
  • teeth are unexpectedly less sensitive, and shinier, the same also being a direct result of composite particle active adhering to the enamel and/or dentin of teeth.
  • Composite particle active may be prepared by forming an aqueous dispersion of core material and an aqueous dispersion of coating material.
  • the pH values of the dispersions are maintained such that the core material and coating material in the dispersions have surface charges of opposite sign wherein mixing of the same does not impact the charge and does allow for coating of the core.
  • a typical method for coating cores is described in greater detail in U.S. Patent No. 5,509,960 . Additional methods (suitable for composite particle active formation) includes the Stöbar method which may be used to make sub-micron sized particles having surface modifications, as well as methods which employ heterogeneous nucleation techniques to coat core materials.
  • Still another method which may be used is one where core component is heated with solvent like water to form a slurry after which silicate or other anionic precursor reagents may be added with pH adjusters and metal salts to produce the desired composite particles for use in this invention.
  • silicate or other anionic precursor reagents may be added with pH adjusters and metal salts to produce the desired composite particles for use in this invention.
  • Such a slurry-based method is further described in commonly-owned patent application, entitled, Composite Particles and Method for Making the Same, identified as G6016(C) and incorporated herein by reference.
  • the oral care composition of this invention is a toothpaste or gel
  • the same typically has a viscosity from about 50,000 to 180,000 centipoise, and preferably, from 60,000 to 170,000 centipoise, and most preferably, from 65,000 to 165,000 centipoise, taken at room temperature with a Brookfield Viscometer, Spindle No. 4.
  • the composition may be packaged in a conventional plastic laminate, metal tube or a single compartment dispenser.
  • the same may be applied to dental surfaces by any physical means, such as a toothbrush, fingertip or by an applicator directly to the sensitive area.
  • Solid dosage form types include pastilles, lozenges, chewing gums, tablets, mouthstrips, balms, and the like. These may be contained in conventional packaging desirable for consumer use.
  • a dual phase aqueous-based oral care composition for benefitting teeth and consistent with this invention was made by mixing the ingredients below under conditions of moderate shear, atmospheric pressure and ambient temperature.
  • the compositions made were suitable for use with a toothbrush, and when combined about equally were not gritty and resulted in an excellent ribbon when applied to a toothbrush.
  • the combined compositions, which resulted in the oral care composition of this invention, had consumer acceptable taste characteristics.
  • Calcium Comprising Phase Ingredients Percent by Weight Sorbitol (70%) 20.0 Water balance Preservative 1.0 Sodium monofluorophosphate 1.1 Sweetener (artificial) 0.2 Calcium silicate* 20.0 Abrasive silica 6.0 Thickening silica (fumed silica) 2.5 Calcium silicate coated titanium dioxide** 4.00 Flavor 0.9 Sodium carboxymethyl cellulose 0.6 Sodium lauryl sulphate (30%) 6.60 * as supplied by Ineos Silicas, Ltd.
  • Phosphate Comprising Phase Ingredients Percent by Weight Sorbitol (70%) 55.0 Trisodium phosphate 7.6 Water Balance Polyethylene glycol (1500) 2.0 Sodium monofluorophosphate 1.1 Sweetener (artificial) 0.27 Color 0.002 Abrasive silica 12.0 Monosodium phosphate 6.4 Thickening silica (fumed silica) 3.5 Sodium lauryl sulphate 30% 6.6 Flavor 1.2 Sodium carboxymethyl cellulose 0.5
  • Enamel and dentin blocks (3 cm 2 ) were polished for at about 5 minutes using silicone carbide abrasive paper (1200 grit).
  • the dentin blocks were acid etched for 60 seconds using 36% phosphoric acid, followed by a water wash.
  • the blocks were purchased from a commercial supplier.
  • a slurry comprising 20% by weight calcium silicate and 4% by weight composite particle active (similar to the one described in Example 1) were added to a water balance to make a slurry.
  • a sodium phosphate slurry was made by adding 20% by weight sodium phosphate to a water balance.
  • the resulting slurries were homogenized for about 10 minutes using conventional stirring apparatus in order to yield homogeneous compositions.
  • the homogenized slurries were poured into petri dishes. Enough was used to cover the surface of the blocks which were placed in the dishes. The blocks were brushed with a toothbrush for 1 minute and incubated in the slurry for one minute. The blocks were subsequently washed with distilled water three times and further incubated in simulated oral cavity fluid for at about 2 hours in a 37°C water bath. Treatment for each block was repeated 14 times.
  • Figure 1A shows a scanning electron microscopy image of the enamel block after one treatment.
  • Composite particle active (circled) surprisingly is shown adhering to the surface of the enamel block after one treatment.
  • Figure 1 B shows an energy dispersive x-ray image (elemental maps, Ti Ka1, 20KV) of the same block.
  • Composite particle active is shown as bright dots (circled) surprisingly adhering well to the enamel block after one treatment.
  • Figure 2A shows a scanning electron microscopy image of the enamel block after 14 treatments and Figure 2B shows an energy dispersive x-ray image of the same block having received fourteen treatments.
  • the results unexpectedly demonstrate excellent adhesion of the composite particle active to the enamel surface.
  • Figure 3A shows a scanning electron microscopy image of the dentin block after one treatment.
  • Composite particle active surprisingly is shown adhering to the surface of the dentin.
  • Figure 3B shows an energy dispersive x-ray image (elemental maps, Ti Ka1 20KV) of the same block.
  • Composite particle active surprisingly is shown adhering to the dentin block.
  • Figure 4A shows a scanning electron microscopy image of the dentin block after 14 treatments and Figure 4B shows an energy dispersive x-ray image of the same block having received the fourteen treatments.
  • the results unexpectedly demonstrate excellent adhesion of the composite particle active to the dentin surface.
  • Example 1 To investigate the whitening effect of the illustrative dual phase oral care composition of Example 1, the following in vitro test was performed.
  • the composition of Example 1 was applied to the surface of the cleaned teeth (Group I) using cotton buds.
  • the cleaned teeth were incubated in simulated oral fluid for about 2 hours.
  • the teeth were subject to 14 cycles of the above treatment.
  • Simulated oral care fluid was made by combining the following: Simulated Oral Fluid Ingredient Amount NaCl 16.07g NaHCO 3 0.7g KCI 0.448g K 2 HPO 3 *H 2 O 3.27g MgCl 2 *6H 2 O 0.622g 1M HCl 40ml CaCl 2 0.1998g Na 2 SO 4 0.1434g Buffer Adjust pH to 7.0 Water Balance to 2L
  • Group B subjects were given the dual phase oral care composition of Example 1 and consistent with this invention;
  • Group A subjects were given a dual phase composition similar to the one described in Example 1 except that 30% by weight calcium silicate was used and no composite particle active was employed.
  • Group C (the control group) subjects brushed teeth with commercially available toothpaste compositions deplete of active associated with tooth remineralization.

Landscapes

  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Organic Chemistry (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Cosmetics (AREA)
EP11707437.7A 2010-09-10 2011-03-11 Oral care compositions for benefiting teeth Active EP2613756B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN2010001395 2010-09-10
PCT/EP2011/053741 WO2012031786A2 (en) 2010-09-10 2011-03-11 Oral care compositions for benefiting teeth

Publications (2)

Publication Number Publication Date
EP2613756A2 EP2613756A2 (en) 2013-07-17
EP2613756B1 true EP2613756B1 (en) 2017-08-02

Family

ID=44625337

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11707437.7A Active EP2613756B1 (en) 2010-09-10 2011-03-11 Oral care compositions for benefiting teeth

Country Status (6)

Country Link
US (1) US20130171221A1 (pt)
EP (1) EP2613756B1 (pt)
CN (2) CN103079526A (pt)
BR (1) BR112013003526B8 (pt)
MX (1) MX337434B (pt)
WO (1) WO2012031786A2 (pt)

Families Citing this family (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MX354227B (es) 2012-12-24 2018-02-19 Colgate Palmolive Co Composición para el cuidado oral.
CN103330652B (zh) * 2013-07-18 2015-05-13 广州薇美姿实业有限公司 一种口腔用组合物及其应用
WO2015036277A1 (en) * 2013-09-10 2015-03-19 Unilever N.V. Oral care composition
CN105517633B (zh) * 2013-09-10 2019-06-18 荷兰联合利华有限公司 口腔护理组合物
US10010491B2 (en) 2013-09-10 2018-07-03 Conopco Inc. Oral care composition
CN105517530B (zh) * 2013-09-10 2019-08-27 荷兰联合利华有限公司 口腔护理组合物
NO2926797T3 (pt) 2014-03-31 2018-02-03
US9895354B2 (en) 2014-04-04 2018-02-20 University Of Kentucky Research Foundation Bilayered calcium sulfate/calcium phosphate space-making composites with multiple drug delivery capabilities
EA032745B1 (ru) * 2014-06-09 2019-07-31 Юнилевер Н.В. Композиции для ухода за полостью рта
CN107635533A (zh) * 2015-05-13 2018-01-26 荷兰联合利华有限公司 口腔护理组合物
WO2016180601A1 (en) 2015-05-13 2016-11-17 Unilever N.V. Oral care composition
CN107743386A (zh) * 2015-06-05 2018-02-27 荷兰联合利华有限公司 口腔护理装置
US20180140520A1 (en) * 2015-06-05 2018-05-24 Conopco, Inc., D/B/A Unilever Oral care device
EP3302405B1 (en) 2015-06-05 2023-08-23 Unilever IP Holdings B.V. Oral care device
EA036458B1 (ru) 2015-11-10 2020-11-12 Юнилевер Н.В. Композиция для ухода за полостью рта
EP3175835A1 (en) 2015-12-04 2017-06-07 Omya International AG Oral care composition for remineralisation and whitening of teeth
WO2019133828A1 (en) * 2017-12-31 2019-07-04 Papazian Mihran Spherificated dental medicament compositions
EP3849507A1 (en) 2018-09-12 2021-07-21 Unilever Global Ip Limited Oral care composition
WO2020212159A1 (en) 2019-04-17 2020-10-22 Unilever Plc Oral care product
EP3882315A1 (en) 2020-03-20 2021-09-22 Omya International AG Surface-treated magnesium ion-containing materials as white pigments in oral care compositions
EP3733154A1 (en) 2019-05-03 2020-11-04 Omya International AG Magnesium ion-containing materials as white pigments in oral care compositions
EP3733786A1 (en) 2019-05-03 2020-11-04 Omya International AG Surface-treated magnesium ion-containing materials as white pigments in oral care compositions
TW202042781A (zh) 2019-05-03 2020-12-01 瑞士商歐米亞國際公司 在口腔保健組成物中作為白色顏料的經表面處理之含鎂離子材料
EP3888619A1 (en) 2020-04-02 2021-10-06 Unilever Global IP Ltd Oral care device
EP3888622A1 (en) 2020-04-02 2021-10-06 Unilever Global IP Ltd Oral care system
EP3888621A1 (en) 2020-04-02 2021-10-06 Unilever Global IP Ltd Oral care device
EP3888620A1 (en) 2020-04-02 2021-10-06 Unilever Global IP Ltd Oral care system
EP3888623A1 (en) 2020-04-02 2021-10-06 Unilever Global IP Ltd Oral care system
CN115887251B (zh) * 2022-12-15 2023-07-04 金三江(肇庆)硅材料股份有限公司 一种二氧化硅-硫酸钙复合颗粒及其制备方法和应用

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008015117A2 (en) * 2006-08-01 2008-02-07 Unilever Plc Biomaterials, their preparation and use

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4108978A (en) * 1971-10-20 1978-08-22 Beecham Inc. Dental compositions
US4083955A (en) 1975-04-02 1978-04-11 The Procter & Gamble Company Processes and compositions for remineralization of dental enamel
SE507731C2 (sv) 1988-12-29 1998-07-06 Colgate Palmolive Co Antibakteriell oral antiplaquekomposition
GB9211822D0 (en) 1992-06-04 1992-07-15 Tioxide Group Services Ltd Composite pigmentary material
AU6947294A (en) * 1993-05-19 1994-12-12 Church & Dwight Company, Inc. Oral care compositions containing zinc oxide particles
US5605675A (en) 1995-06-06 1997-02-25 Enamelon Inc. Processes and compositions for remineralization and prevention of demineralization of dental enamel
US5735942A (en) 1996-02-07 1998-04-07 Usbiomaterials Corporation Compositions containing bioactive glass and their use in treating tooth hypersensitivity
US6159448A (en) * 1996-09-27 2000-12-12 Enamelon, Inc. Products and methods for the remineralization and prevention of demineralization of teeth
IN191261B (pt) 1997-09-18 2003-10-18 Univ Maryland
US20090264291A1 (en) 1998-02-23 2009-10-22 Etienne Soudant Compositions comprising anti-proliferative agents and use thereof
US6120754A (en) 1998-03-11 2000-09-19 Chesebrough-Pond's Usa Co., Division Of Conopco, Inc. Remineralization of teeth
US5858333A (en) * 1998-08-07 1999-01-12 Enamelon, Inc. Two-part oral products and methods of using same to remineralize teeth
US6436370B1 (en) * 1999-06-23 2002-08-20 The Research Foundation Of State University Of New York Dental anti-hypersensitivity composition and method
US7838037B2 (en) * 1999-11-17 2010-11-23 Tagra Biotechnologies Ltd. Method of microencapsulation
JP3905836B2 (ja) * 2000-10-13 2007-04-18 ブロック ドラッグ カンパニー インコーポレイテッド 不適合成分をデリバリーするための無水歯磨き処方
EP1731132B1 (en) * 2000-10-13 2008-12-10 Block Drug Company, Inc. Dental compositions for hypersensitive teeth
US20080050408A1 (en) * 2004-11-26 2008-02-28 Discus Dental, Llc Dental Whitening Compositions
EP2089040B1 (en) * 2006-12-05 2012-01-04 Unilever PLC Oral care product

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008015117A2 (en) * 2006-08-01 2008-02-07 Unilever Plc Biomaterials, their preparation and use

Also Published As

Publication number Publication date
MX337434B (es) 2016-03-04
BR112013003526B8 (pt) 2018-02-27
US20130171221A1 (en) 2013-07-04
WO2012031786A2 (en) 2012-03-15
BR112013003526A2 (pt) 2016-06-28
CN103079526A (zh) 2013-05-01
MX2013002721A (es) 2013-04-03
CN107582413A (zh) 2018-01-16
BR112013003526B1 (pt) 2018-01-30
EP2613756A2 (en) 2013-07-17
WO2012031786A3 (en) 2012-07-05

Similar Documents

Publication Publication Date Title
EP2613756B1 (en) Oral care compositions for benefiting teeth
EP2613850B1 (en) Composite particle active and method for making the same
EP2699217B1 (en) Tooth remineralizing oral care compositions
EP3043868B1 (en) Oral care composition
WO2011109919A1 (en) Stable oral care compositions
CN111093604B (zh) 口腔护理组合物
CN110997072B (zh) 口腔护理组合物
EP3648731B1 (en) Oral care composition
WO2018073062A1 (en) Oral care composition
CN110545784B (zh) 口腔护理组合物
EP3554459B1 (en) Oral care composition
EP3500232B1 (en) Oral care composition
EP3374031B1 (en) Oral care composition
CN111093603B (zh) 口腔护理组合物
EP3352723B1 (en) Oral care composition
WO2020099068A1 (en) Oral care composition
CN110573131B (zh) 口腔护理组合物

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20130208

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20141212

REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 602011040123

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: A61K0008040000

Ipc: A61K0008190000

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RIC1 Information provided on ipc code assigned before grant

Ipc: A61K 8/29 20060101ALI20170404BHEP

Ipc: A61K 8/19 20060101AFI20170404BHEP

Ipc: A61Q 11/00 20060101ALI20170404BHEP

Ipc: A61K 8/27 20060101ALI20170404BHEP

INTG Intention to grant announced

Effective date: 20170511

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 913675

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170815

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602011040123

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20170802

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 913675

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170802

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170802

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170802

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170802

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170802

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170802

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171102

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170802

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170802

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171103

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171102

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170802

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170802

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171202

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170802

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170802

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170802

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170802

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602011040123

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170802

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170802

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170802

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20180503

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170802

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170802

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20180331

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180311

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180311

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180331

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180331

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180311

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20110311

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170802

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170802

Ref country code: MK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170802

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: TR

Payment date: 20200311

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170802

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 602011040123

Country of ref document: DE

Owner name: UNILEVER GLOBAL IP LIMITED, WIRRAL, GB

Free format text: FORMER OWNER: UNILEVER N.V., ROTTERDAM, NL

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

Free format text: REGISTERED BETWEEN 20220127 AND 20220202

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20230327

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20230323

Year of fee payment: 13

Ref country code: GB

Payment date: 20230321

Year of fee payment: 13

Ref country code: DE

Payment date: 20220620

Year of fee payment: 13

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230426